Process for dyeing locks of human hair with tetragolium salts

ABSTRACT

A process and composition for dyeing keratinic fibers, particularly, human hair, in which tetrazolium salts are applied to the fibers in a colorless oxidized state and reduced to colored insoluble formazanes by reducing agents. The reducing agents are used so that the keratinic bonds are not disrupted and can be used at the same time that a permanent wave process is applied. Also, various shades can be obtained using leuco derivative dyes which become oxidized when functioning as reducing agents.

United States Patent Kalopissis et a].

[ 1 Mar. 14, 1972 [54] PROCESS FOR DYEING LOCKS OF HUMAN HAIR WITHTETRAGOLIUM SALTS lnventors: Gregoire Kalopissis, Paris; Andree Bugaut,

Boulogne, both of France Assignee: Societe Anonyme dite: LOreal Filed:Aug. 5, 1968 Appl. No.: 749,958

Foreign Application Priority Data Aug. 8, 1967 Luxembourg ..54,267 Dec.4, 1967 Luxembourg ...55,016

U.S.Cl ..8/10,8/10.1,8/11,

8/17, 8/l27.51, 8/41 B, 8/46, 260/308 D, 260/193 Int. Cl ..D06p 3/04,D06p 3/08 Field ofSearch ..8/127.51,10,10.1,4l,46,

[56] References Cited UNITED STATES PATENTS 3 ,297,709 1/1967 Davis..260/ 308 3,185,567 5/1965 Rogers ..96/3 3,257,205 6/ 1966 Cassiers eta1. ..96/95 X 3,396,736 8/1968 Shansky ..8/10 X Primary ExaminerGeorgeF. Lesmes Assistant Examiner-Patricia C. lves Attorney-Holcombe,Wetherill & Brisebois [57] ABSTRACT 6 Claims, No Drawings PROCESS FORDYEING LOCKS OF HUMAN HAIR WITH TETRAGOLIUM SALTS In a known method ofdyeing keratinic fibers, compositions are used which contain compoundswhich are colorless and soluble in water when in a reduced state, butcapable of being transformed, when oxidized, into colored pigments whichare insoluble in water.

Among these coloring compositions are those based on oxidation dyes andon vat dyes.

The present invention relates to the use of compounds for dyeingkeratinic fibers which, in contradistinction to those heretofore in use,are colorless and soluble in water when oxidized, but are insoluble ornearly so in water, and very strongly colored when reduced.

The dyes of this type have several advantages when used to dye keratinicfibers, and particularly human hair. When in their colorless, oxidizedform, they penetrate the keratinic fibers very well and have a greatafiinity for them, so that the hair may be washed immediately afterimpregnation with one of these colorless dyeing compositions, and thecolor then developed by reduction.

It is an object of the present invention to provide a new method ofdyeing keratinic fibers and especially human hair characterized by thestep of impregnating the hair with a composition containing at least onetetrazolium salt responding to the formula:

in which:

n is a whole number equal to 1 or 2,

R and R" represent aromatic radicals which may be substituted by groupssuch as nitro, methoxy and halogen groups;

R, regardless of the value of n, represents hydrogen, an

alkyl radical, an aromatic radical, which may be substituted by suchgroups as nitro, methoxy, or halogen groups, a heterocyclic remainder oran N=N-Ar remainder in which Ar represents an aromatic group;

Y represents:

hydrogen, when n=l or a radical responding to the formula when n=2.

A represents an anion, such for example, as a halide,

methosulfate, sulfate, or acetate.

After rinsing the fibers or the hair, if desired, thecolor is broughtout by applying a reducing solution which transforms the saidtetrazolium salt or salts into colored insoluble formazanes, accordingto the reaction:

The reducing agents which may be used in accordance with 75 I 3,3 .929tent r the s e sy whis h e y qit e vsi tion potentials lower than thoseof formazane/tetrazolium salt systems.

The reducing agents which may be used in carrying out the invention maybe those which do not have any effect on the structure of the keratin ofthe hair, and specifically not on the S-S bonds, that is to say, softreducing agents such as ascorbic acid, hydrazine, dithionic acids, andthe reductones.

It is also possible to use reducing agents such as thiols orborohydrides, which can disrupt the SS bonds of the keratin, butpreferably in such weak concentrations, that they have practically nochemical effect on the hair.

Colorless compounds which do not react with the keratin and which aretransformed into colored compounds by oxidation, such as leucoderivatives, or oxidation dyes may also be used as reducing agents.

In this method the reducing agents of the leuco-derivative type or theoxidation dyes may act as shade varying means.

In accordance with the present invention a colored permanent wave may beeffected by utilizing the properties of tetrazolium salts.

In one alternative method, the hair may first be treated with aconventional reducing agent, rinsed, and treated with a solution oftetrazolium salt which, by reacting with the reducing groups in thehair, are transformed into formazane and develop a color. If so desired,an oxidizing agent may then be applied to carry out the second step of aconventional permanent.

In a second alternative method a solution of tetrazolium salts isapplied to the hair, after which a conventional permanent waving processis carried out, that is to say, a reducing solution is applied, whichtransforms the tetrazolium salts into forrnazanes and so develops thecolor. The second step of a permanent waving process, that is to say,the application of a conventional oxidizing agent, may then be carriedout, if desired.

A further object of the invention is to provide a hair dyeingcomposition characterized by the fact that it contains at least onetetrazolium salt, as above defined.

Among the tetrazolium salts which may be used in accordance with thepresent invention are the following, but this list is not exhaustive:

3-para nitrophenyl-2,5 diphenyl tetrazolium chloride responding to theformula:

MGM Q 3,3'-para (di-orthomethoxy) diphenylene-2,2', 5,5-

tetraphenyl-ditetrazolium dichloride responding to the formula:

ew 4) CH; CH:

,3"-para (di-orthomethoxy) diphenylene-Z ,2'-diphenyl--paradiphenylene-2,2',5,5tetraphenyl-ditetrazolium e rqnsiq tqtt fe s e11506- l c-ciHr [01-12 In a preferred embodiment of the invention thecomposition contains from 0.1 to 10 percent of tetrazolium salts.

In one specific embodiment the pH value of the composition is basic,that is to say, greater than 7.

The composition according to the invention may also contain anyadditives which are conventionally used in dyeing solutions. They maytake the form of aqueous or hydroalcoholic solutions, creams, gels, oraerosols.

Among the tetrazolium salts which may be used in carrying out theinvention, a certain number have the characteristic of formingphotosensitive formazanes, that is to say formazanes which are unstablein the presence of light. in this particular case the colors obtainedare transient and make it possible to apply shades to the hair which areof short duration, and are then eliminated without any need to resort toa bleach.

The transient dyeing compounds according to the invention have theadvantage over those transient dyeing compounds heretofore known thatthey degrade progressively with out changing the color of the hair,their disappearance being evidenced only by a progressive decrease inthe intensity of the color.

In order that the object of the invention may be better understood,several methods of carrying it out will now be described, purely by wayof illustration and example.

EXAMPLE 1 The following solution is prepared:

3-p-nitrophenyl2.5'diphenyl tetrazaliurn chloride 3.8 g Nl-l OH q.s.p.pH l0 water, q.s.p. [00 cc.

This solution is applied to 90 percent white hair, and left to act for15 minutes, after which the hair is rinsed.

10 cc. of 3 percent sodium ascorbate is then applied and left to act for15 minutes.

The hair is then rinsed and shampooed.

The result is a violet red shade.

EXAMPLE 2 A solution A having the following composition is prepared:

Jpara nitrophenyl-lj-diphenyl tetrazolium chloride water, q.s.p.

EXAMPLE 3 A lock of bleached hair is impregnated with the abovepregnatedwith the following reducing solution for pennanent waving:

thioglycnlic acid 5 g. ammonia q.s.p. pH 7.7 water q.s.p. 100 g.

This is left to act for 7 minutes. The hair is then rinsed withdescribed solution A for 15 minutes, as indicated in Example 6 5 1. Itis then rinsed in clear water, and a spraying solution having thefollowing composition is prepared:

A deep red color is produced at once, and resists subsequentshampooings.

clear water, the permanent fixed with solution A for 5 minutes, andrinsed.

The result is a lock which is curly and deep red in color. Both thecolor and the curl resist subsequent shampooing.

EXAMPLE 5 The following solutions are prepared:

Solution l: 3-para nitro phcnyblfi diphen yl tetrazoliurn chloride 0.395. water, q.s.p. 100 3.

Solution 2: hydrazine 0.3 5. water. q.s.p. 100 g.

The two above solutions are mixed in equal quantities and a lock ofbleached hair is immediately colored. in this mixture the 3-para nitrophenyl-2,5-diphenyl tetrazolium chloride and the hydrazine are inequimolecular proportions. The pH of the mixture is near neutrality. Thesolution is left to act for IS minutes and the hair is rinsed andshampooed. An orange red coloration results.

EXAMPLE 6 The following dyeing composition is prepared:

LIV-para (di-orthornethoxy) diphenylenc-2,2', 5 ,5'-tetraphenylditcu'azoliurn chloride 1 5. water, q.s.p. 100 g.

This solution is applied to percent white hair, and left to act for 15minutes, and the hair rinsed. The lock is not colored. The followingsolution is then prepared:

fonnamidine rulfinic acid (Manofast) l 5. Nil NaOH solution q.s.p. pH 10water q.l.p. g.

This is left to act for 5 minutes. The hair is then rinsed andshampooed. A gray violet color results.

EXAMPLE 7 The following solutions are prepared:

Solution l: 3,3'-para (di-orthornethoxy) diphenylene-LZ ',S,S -tetmvphenyl-ditctrazolium dichloride lwater q.s.p. N30 Solution 2:alloxantine 0.32 g.

5 N NaOH q.a.p. pH 10 water. q.r.p. I00 5.

When about to dye, the two solutions are mixed in equal quantities, sothat they are in equimolecular proportions.

A lock of 90 percent white hair is impregnated with this mixture for 15minutes, rinsed, and shampooed. The result is a giayg violet a littlemore intense and more violet than in Exam-, p e

EXAMPLE 8.

The following composition is prepared:

A lock of 90 percent white hair is impregnated with this solution, andleft to act for 15 minutes. The hair is then rinsed.

A 3 percent solution of sodium hydrosulfite, brought to pH by theaddition of sodium hydroxide is then applied. This is left to act for 5minutes, after which the hair is rinsed and shampooed. A deep blue greyresults.

EXAMPLE 9 The following solutions are prepared:

Just before application to the hair, the two solutions are mixed inequal quantities, i.e., in equimolecular proportions. The mixture has apH value of about 7.

This mixture is applied to 90 percent white hair, and left to act forminutes. The hair is then rinsed and shampooed. A deep grey blackresults.

What is claimed is:

l. A process for dyeing locks of human hair, which comprises the step ofimpregnating the hair with at least one composition containing fromabout 0.1 to 10 percent of a tetrazolium salt responding to the formula:

in which:

n is a whole number between 1 and 2 inclusive,

R is a radical selected from the group consisting of phenylene and aphenylene substituted by a substituent selected from the groupconsisting of nitro and methoxy radicals;

R" is a radical selected from the group consisting of phenyl and aphenyl substituted by a substituent selected from the group consistingof nitro and methoxy radicals;

R is selected from the group consisting of hydrogen, phenyl, and aphenyl radical substituted by a substituent selected from the groupconsisting of nitro and methoxy radicals;

Y is selected from the group consisting of hydrogen, when n=1, and, whenn=2,

a radical corresponding to the following formula:

and developing the color by reducing the tetrazolium salt in the hairwith a reducin solution or H 0;.

2. A process accor ing to claim f, in WhlCh the reducing solutioncontains a reducing agent selected from the group consisting of ascorbicacid, hydrazine, dithionic acids, reductones, borohydrides, thiols,sodium ascorbates, forrnamidine sulfinic acid, alloxanthine,aminohydroquinone hydrobromide, and sodium hydrosulfite.

3. A process according to claim 1, in which the hair is rinsed withwater before applying the reducing solution.

4. A process according to claim 1, in which the tetrazolium salt ismixed, immediately before applying to the hair, with the solutioncontaining the reducing agent.

5. A process according to claim 1, in which the dyeing of the hair iscombined with a permanent waving process, the hair being firstimpregnated with a reducing agent, conventionally used in the first stepof a permanent waving process, rinsed, and then treated with thetetrazolium salt and then neutralized.

6. A process according to claim 1, in which the dyeing of the hair iscombined with a permanent waving process, the hair being firstimpregnated with the composition containing the tetrazolium salt andthen treated with a reducing agent conventionally used in the first stepof a permanent waving process and then the hair is neutralized.

2. A process according to claim 1, in which the reducing solutioncontains a reducing agent selected from the group consisting of ascorbicacid, hydrazine, dithionic acids, reductones, borohydrides, thiols,sodium ascorbates, formamidine sulfinic acid, alloxanthine,aminohydroquinone hydrobromide, and sodium hydrosulfite.
 3. A processaccording to claim 1, in which the hair is rinsed with water beforeapplying the reducing solution.
 4. A process according to claim 1, inwhich the tetrazolium salt is mixed, immediately before applying to thehair, with the solution containing the reducing agent.
 5. A processaccording to claim 1, in which the dyeing of the hair is combined with apermanent waving process, the hair being first impregnated with areducing agent, conventionally used in the first step of a pErmanentwaving process, rinsed, and then treated with the tetrazolium salt andthen neutralized.
 6. A process according to claim 1, in which the dyeingof the hair is combined with a permanent waving process, the hair beingfirst impregnated with the composition containing the tetrazolium saltand then treated with a reducing agent conventionally used in the firststep of a permanent waving process and then the hair is neutralized.